EP2597123A1 - Aqueous adhesive for fibrous and/or granular substrates - Google Patents

Abstract

Aqueous binder comprises (a) at least one organic compound having at least two primary amino groups (polyamine) and (b) at least one saccharide compound with a weight ratio of at least 1:99-80:20. Independent claims are also included for: (1) producing a molded body from granular and/or fibrous substrates, comprising applying the above aqueous binder to the granular and/or fibrous substrate, optionally bringing grained and/or fibrous substrate treated with the aqueous binder into a mold, and subjecting the treated granular and/or fibrous substrate to a thermal treatment step at a temperature of >= 110[deg] C; and (2) the molded body obtainable by the above method.

Description

1. a) wenigstens eine organische Verbindung, welche wenigstens zwei primäre Aminogruppen aufweist [Polyamin A], und
2. b) wenigstens eine Saccharidverbindung S, wobei
3. c) das Gewichtsverhältnis des wenigstens einen Polyamins A zur wenigstens einen Saccharidverbindung S 1:99 bis 80:20 beträgt.

The present invention is an aqueous binder for granular and / or fibrous substrates containing as active ingredients

1. a) at least one organic compound which has at least two primary amino groups [polyamine A], and
2. b) at least one saccharide compound S, wherein
3. c) the weight ratio of the at least one polyamine A to at least one saccharide compound S is 1:99 to 80:20.

The present invention furthermore relates to a process for the production of moldings from granular and / or fibrous substrates using the aforementioned binder and the molded articles produced by the process.

The solidification of fibrous and / or granular substrates, in particular in sheet-like structures, such as fiber webs, fiberboard, chipboard or more complex non-planar moldings, etc., often takes place chemically using a polymeric binder. To increase the strength, in particular the wet strength and heat resistance, binders are often used which contain formaldehyde-releasing crosslinkers. But there is the danger of unwanted formaldehyde emission.

To avoid formaldehyde emissions, numerous alternatives to the previously known binders have already been proposed. So are from the US-A 4,076,917 Binders known which contain carboxylic acid or carboxylic anhydride-containing polymers and β-hydroxyalkylamides as crosslinking agents. A disadvantage is the relatively complicated production of β-hydroxyalkylamides.

From the EP-A-445578 For example, sheets of particulate materials such as glass fibers are known in which mixtures of high molecular weight polycarboxylic acids and polyhydric alcohols, alkanolamines or polyhydric amines act as binders.

From the EP-A-583086 are formaldehyde-free, aqueous binders for the production of fiber webs, in particular glass fiber webs known. The binders contain a polycarboxylic acid having at least two carboxylic acid groups and optionally also anhydride groups and a polyol. These binders require a phosphorus-containing reaction accelerator to achieve sufficient strengths of the glass fiber webs. It should be noted that the presence of such a reaction accelerator can only be dispensed with, when a reactive polyol is used. As highly reactive polyols β-hydroxyalkylamides are mentioned.

The EP-A-651088 describes corresponding binders for substrates made of cellulose fiber. These binders necessarily contain a phosphorus-containing reaction accelerator.

The EP-A-672 920 describes formaldehyde-free binding, impregnating or coating compositions which comprise a polymer which is composed of 2 to 100% by weight of an ethylenically unsaturated acid or an acid anhydride as comonomer and contains at least one polyol. The polyols are substituted triazine, triazinetrione, benzene or cyclohexyl derivatives, the polyol radicals always being in the 1,3,5-position of the mentioned rings. Despite a high drying temperature, only low wet tensile strengths are achieved with these binders on glass fiber nonwovens.

The DE-A-2214450 describes a copolymer which is composed of 80 to 99% by weight of ethylene and 1 to 20% by weight of maleic anhydride. The copolymer is used, together with a crosslinking agent, in powder form or in dispersion in an aqueous medium for surface coating. As the crosslinking agent, an amino group-containing polyhydric alcohol is used. However, to effect cross-linking, it must be heated up to 300 ° C.

From the US-A 5,143,582 For example, the production of heat-resistant nonwoven materials using a thermosetting, heat-resistant binder is known. The binder is free of formaldehyde and is obtained by mixing a carboxylic acid group, carboxylic acid anhydride group or carboxylic acid salt group-having polymer and a crosslinking agent. The crosslinker is a β-hydroxyalkylamide or a polymer or copolymer thereof. The crosslinkable with the β-hydroxyalkylamide polymer is, for example, composed of unsaturated mono- or dicarboxylic acids, salts of unsaturated mono- or dicarboxylic acids or unsaturated anhydrides. Self-curing polymers are obtained by copolymerization of the β-hydroxyalkylamides with monomers containing carboxyl groups.

In the US-A 2004/82689 formaldehyde-free aqueous binders for the production of fiber webs, in particular glass fiber webs, disclosed which consist essentially of a polymeric polycarboxylic acid, a polyol and an imidazoline derivative. The resulting bonded fiber webs should have a reduced water absorption. Nonspecifically, both nitrogen-containing and nitrogen-free polyols are disclosed, but in particular the nitrogen-containing triethanolamine is described as being preferred. As specific imidazoline derivatives are mentioned reaction products of a fatty acid with aminoethylethanolamine or diethylenetriamine. The disclosed aqueous binder compositions contain a phosphorus-containing reaction accelerator.

According to the WO 99/09100 thermally curable compositions and their use as formaldehyde-free binders for the production of moldings are disclosed, which in addition to an alkanolamine having at least two OH groups, a polymer 1 which contains ≦ 5% by weight and a further polymer 2 which contains ≥ 15% by weight of an α, β-ethylenically unsaturated mono- or dicarboxylic acid in copolymerized form.

Furthermore, the WO10 / 34645 aqueous binder systems for granular and / or fibrous substrates, which as active ingredients, a polymer 1, containing ≥ 5.5 wt .-% and ≤ 20 wt .-% of an α, β-ethylenically unsaturated mono- or dicarboxylic acid in copolymerized form, a Polymer 2, containing ≥ 40 wt .-% of an α, β-ethylenically unsaturated mono- or dicarboxylic acid in copolymerized form and a polyol compound having at least two hydroxyl groups.

In a priority and not pre-published European patent application with application number 11154347.6 aqueous binders for granular and / or fibrous substrates are disclosed, which in addition to a carboxylic acid group-containing polymer and a polyol containing essential salt compound. These salt-containing binder liquors have an advantageous effect on the wet tensile strength and the breaking strength at 180 ° C. of the fiber webs bound thereto.

Also disclosed in priority and unpublished European patent application Ser. No. 11159420.6 are aqueous binders for granular and / or fibrous substrates which comprise as essential components a polymeric polycarboxylic acid, a nitrogen-free polyol compound having at least two hydroxyl groups and a hydroxy-free organic nitrogen compound having a pK _B value ≤ 7 included.

In the case of saccharide-containing aqueous binder compositions for granular and / or fibrous substrates, the following state of the art can be assumed.

In the EP-A 649870 discloses mixtures of polycarboxylic acids and saccharide compounds in the weight ratio of 95: 5 to 20:80 for the production of polymer films with gas barrier effect.

The EP-A 911361 discloses aqueous binder systems for granular and / or fibrous substrates containing a polycarboxy polymer having a weight average molecular weight of at least 1000 g / mol and a polysaccharide having a weight average molecular weight of at least 10,000 g / mol, the amounts of which are such that the equivalence ratio of carboxyl groups to hydroxyl groups is 3: 1 to 1:20.

Furthermore, the EP-A 1578879 aqueous binder compositions for coating glass fibers, comprising a polycarboxy polymer, a polyhydric alcohol having at least two hydroxyl groups and a so-called water-soluble extender, being proposed as a water-soluble extender in particular polysaccharides having an average molecular weight less than 10,000 g / mol.

The WO 2008/150647 discloses aqueous binder systems for producing fiber mats, comprising a urea / formaldehyde resin and an aqueous copolymer dispersion whose copolymer is essentially composed of styrene, alkyl acrylates or methacrylates, acrylonitrile and an optionally substituted acrylamide. Optionally, the aqueous copolymer dispersion may still contain starch.

Also the US-A 2009/170978 discloses aqueous binder systems for nonwoven fabrics, comprising an aqueous copolymer dispersion whose copolymer contains between 5 and 40% by weight of at least one carboxylic acid group-containing monomer in copolymerized form and a natural binder component selected from the group comprising polysaccharides, vegetable proteins, lignins and / or ligninsulfonates.

In a priority and not pre-published European patent application with application number 11161026.7 aqueous binders for granular and / or fibrous substrates are disclosed which, in addition to a saccharide compound, also contain a specific polymer containing nitrile groups and carboxylic acid groups or carboxylic acid amide groups.

However, the moldings produced with the abovementioned compositions, in particular fiber webs, are not always able to fully satisfy the water resistance in cork moldings in all mechanical properties, such as the breaking strength, in particular the wet tear strength of glass fiber webs. Furthermore, the market is increasingly seeking alternative formaldehyde-free binder systems based on renewable raw materials.

The object of the present invention was to provide an alternative formaldehyde-free aqueous binder system based on renewable raw materials for fibrous and / or granular substrates, by which in moldings, such as fiber webs equivalent or improved mechanical properties, in particular the wet tensile strength in glass fiber webs and / or the water resistance in cork moldings result.

Accordingly, the initially defined aqueous binder was found.

The binder according to the invention contains as an essential component at least one organic compound which has at least two primary amino groups [polyamine A].

According to the invention, as polyamines A, it is possible to use all organic compounds which have at least two primary amino groups. In this case, the molecular weight of the polyamines A in the range ≥ 60 and ≤ 10,000,000 g / mol. It is essential that as polyamines A both low molecular weight aliphatic, aromatic or heterocyclic compounds can be used which have at least two primary amino groups, as well as corresponding oligomeric or polymeric compounds which at least two primary Containing amino groups containing monomer in copolymerized form. The low molecular weight, nonpolymeric polyamines A have a molecular weight <500 g / mol, while the oligomeric or polymeric polyamines A have a weight average molecular weight ≥ 500 g / mol. The determination of the weight-average molecular weight of the oligomeric or polymeric polyamines A is familiar to the person skilled in the art and generally takes place within the scope of this document by gel permeation chromatography with defined standards.

Examples of low molecular weight aliphatic, aromatic or heterocyclic polyamines A which may optionally be substituted by one or more C ₁ -C ₁₀ -alkyl groups are linear aliphatic C ₂ -C ₁₀ -amines, such as 1,2-diaminoethane, 1,2 Diaminopropane, 1,3-diaminopropane, 1,2,3-triaminopropane, 1,3-diamino-2-methylpropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,2,3 Triaminobutane, 1,2,4-triaminobutane, 1,2-diamino-3-methylbutane, 1,3-diamino-2-methylbutane, 1,5-diaminopentane, 1,3-diamino-2,2-dimethylpropane, 1 , 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane and their isomeric compounds, cycloaliphatic amines, such as 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1 , 4-Diaminocyclohexane, 2,3-diaminomethylcyclohexane, 2,4-diaminomethylcyclohexane, 2,5-diaminomethylcyclohexane, 2,6-diaminomethylcyclohexane, 3,4-diaminomethylcyclohexane, 3,5-diaminomethylcyclohexane, isophoronediamine, aromatic amines, such as 1,2 diamino benzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,2-diamino-3-methylbenzene, 1,2-diamino-4-methylbenzene, 1,3-diamino-2-methylbenzene, 1,3-diaminobenzene 4-methylbenzene, 1,4-diamino-2-methylbenzene, 1,3,5-triaminobenzene, 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane and as heterocyclic amines, for example 2,3 -Diaminopyridine, 2,4-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 3,5-diaminopyridine, 2,3-diaminofuran, 2,4-diaminofuran, 3,4-diaminofuran , 2,3-diaminopyrrole, 2,4-diaminopyrrole, 3,4-diaminopyrrole, 2,3-diaminothiophene, 2,4-diaminothiophene or 3,4-diaminothiophene. Of course, the low molecular weight polyamines A also include low molecular weight polyalkylenepolyamines having a molecular weight <500 g / mol, such as diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, N-3-aminopropylethylenediamine, N, N, N-tris (3-aminopropyl) amine, N , N'-bis (3-aminopropyl) ethylenediamine-1,2 or corresponding low molecular weight 1, ω-diamines based on ethylene oxide and / or propylene oxide, such as 1,5-diamino-3-oxapentane, 1,8-diamino-3 , 6-diazaoctane or 1,10-diamino-4,7-diazadecane.

In the context of this document, C ₁ - to C ₁₀ -alkyl groups are to be understood as meaning linear or branched alkyl radicals having 1 to 10 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, tert-pentyl n-hexyl, 2-ethylhexyl, n-nonyl or n-decyl be understood.

Suitable low molecular weight polyamines A are advantageously 1,6-diaminohexane, isophoronediamine, diethylenetriamine, dipropylenetriamine and / or N, N'-bis (3-aminopropyl) ethylenediamine-1,2 and particularly advantageously 1,6-diaminohexane, diethylenetriamine and / or N. , N'-bis (3-aminopropyl) ethylenediamine-1,2 used.

Suitable oligomeric or polymeric polyamines A are all organic compounds having a weight average molecular weight ≥ 500 g / mol, which have at least 2 primary amino groups, such as in particular polyethyleneimines, homo- or copolymers based on allylamine and vinylamine units containing homopolymers or copolymers.

The polyethylenimines which can advantageously be used according to the invention are obtainable as catalyst by polymerizing ethyleneimine in the presence of acids, Lewis acids or acids which split off the acids. Such catalysts are, for example, alkyl halides such as methyl chloride, ethyl chloride, propyl chloride, methylene chloride, trichloromethane, carbon tetrachloride or tetrabromomethane. The polyethyleneimines thus prepared have a branched structure with a proportion of primary and tertiary amino groups of about 30% and a proportion of secondary amino groups of about 40%. The polyethyleneimines generally have weight average molecular weights in the range of ≥500 and ≤10,000,000 g / mol, preferably ≥800 and ≤75000 g / mol, and more preferably ≥1000 and ≤10000 g / mol. The production of polyethyleneimines by acid-catalyzed reaction of ethyleneimine is described, for example, in US Pat US-A 2,282,306 or the US-A 3,203,910 disclosed. In addition, compounds containing ethyleneimine units are polymers obtainable by grafting polyamidoamines with ethyleneimine or by grafting polymers of open-chain N-vinylcarboxamides with ethyleneimine. Grafted polyamidoamides are for example from US-A 4,144,123 known.

Typical representatives of polyethyleneimine having a branched structure are available under the trade name Epomin ^® SP-006, Epomin ^® SP-018 or Epomin ^® SP-200 from Nippon Shokubai or Lupasol ^® FG, Lupasol ^® G 20, Lupasol ^® G 35, Lupasol ^® G 100 and Lupasol ^® PS BASF SE known.

Homopolymers containing vinylamine units are obtainable by a two-stage process by polymerization of N-vinylcarboxamides and hydrolysis of the resulting poly (N-vinylcarboxamides) with formation of vinylamine units (compare, for example, in this connection US-A 4,421,602 . US-A 5,334,287 . EP-A 216387 . US-A 5,981,689 . WO 00/63295 . US-A 6,121,409 or US-A 6,132,558 ). Examples of useful N-vinylcarboxamides are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl-acetamide and N-vinylpropionamide. The monomers mentioned can be polymerized either alone, mixed with one another or together with other monomers to form the corresponding copolymers. Preferred as the N-vinylcarboxamide is N-vinylformamide.

Suitable comonomers are all ethylenically unsaturated compounds copolymerizable with the N-vinylcarboxamides. Examples of these are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, N-vinylpyrrolidone, vinyl propionate and vinyl butyrate and vinyl ethers such as C ₁ - to C ₆ -alkyl vinyl ethers, for example methyl or Ethyl vinyl ether. Further suitable comonomers are esters of alcohols having, for example, 1 to 6 carbon atoms, amides and nitriles of ethylenically unsaturated C ₃ - to C ₆ -mono- or C ₄ - to C ₈ -dicarboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate and dimethyl maleate , Acrylamide and methacrylamide as well as acrylonitrile and methacrylonitrile.

Further suitable compounds which can be copolymerized with N-vinylcarboxamides are carboxylic esters of glycols or polyalkylene glycols, in each case only one OH group being esterified, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and acrylic monoesters of polyalkylene glycols having a molecular weight of from 500 to 10000 g / mol. Further suitable comonomers are esters of ethylenically unsaturated carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylamino-propyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylaminobutyl acrylate. The basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or sulfonic acids or in quaternized form. Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride. Further suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids having alkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and tert-butylacrylamide and basic (meth) acrylamides, e.g. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide.

Further suitable comonomers are N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles, e.g. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazo-lin and N-vinyl-2-ethylimidazoline. N-vinylimidazoles and N-vinylimidazolines are used except in the form of the free bases also neutralized or in quaternized form with mineral acids or organic acids, wherein the quaternization is preferably carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Also suitable are diallyldialkylammonium halides, e.g. Diallyl dimethyl ammonium chloride.

• 95 bis 5 mol-%, vorzugsweise 90 bis 10 mol-% mindestens eines N-Vinylcarbonsäureamids, bevorzugt N-Vinylformamid, und
• 5 bis 95 mol-%, vorzugsweise 10 bis 90 mol-% wenigstens eines monoethylenisch ungesättigten Comonomeren

in einpolymerisierter Form. Die Comonomeren sind vorzugsweise frei von Säure-gruppen.The copolymers contain advantageous

• 95 to 5 mol%, preferably 90 to 10 mol% of at least one N-vinylcarboxamide, preferably N-vinylformamide, and
• 5 to 95 mol%, preferably 10 to 90 mol% of at least one monoethylenically unsaturated comonomer

in copolymerized form. The comonomers are preferably free of acid groups.

The polymerization of the aforementioned monomers is usually carried out in the presence of radical-forming polymerization initiators. The homopolymers and copolymers can be obtained by all known processes, for example by solution polymerization in water, alcohols, ethers or dimethylformamide or in mixtures of various solvents, by precipitation polymerization, reverse suspension polymerization (polymerizing an emulsion of a monomer-containing aqueous phase in an oil phase and polymerizing a water-in-water emulsion, for example, in which an aqueous monomer solution is dissolved or emulsified in an aqueous phase and polymerized to form an aqueous dispersion of a water-soluble polymer, such as in US Pat WO 00/27893 described. Following the polymerization, the homo- and co-polymers containing copolymerized N-vinylcarboxamide units are partially or completely hydrolyzed as described below.

• N-Vinylformamid mit
• Vinylformiat, Vinylacetat, Vinylpropionat, Acrylnitril, Methylacrylat, Ethylacrylat und/oder Methylmethacrylat

und anschließende Hydrolyse der Homo- oder der Copolymerisate unter Bildung von Vinylamineinheiten aus den einpolymerisierten N-Vinylformamideinheiten erhältlich sind, wobei der Hydrolysegrad in der Regel ≥ 1 und ≤ 100 mol-%, vorzugsweise ≥ 25 und ≤ 100 mol-%, besonders bevorzugt ≥ 50 und ≤ 100 mol-% und insbesondere bevorzugt ≥ 70 und ≤ 100 mol-% beträgt, jeweils bezogen auf den ursprünglichen Gehalt an nichthydrolysierten N-Vinylcarbonsäureamidgruppen. Der Hydrolysegrad entspricht bei den Homopolymerisaten dem Gehalt an Vinylamingruppen in mol-%. Die Hydrolyse der oben beschriebenen Polymerisate
erfolgt nach bekannten Verfahren durch Einwirkung von Säuren (beispielsweise Mineralsäuren wie Schwefelsäure, Salzsäure oder Phosphorsäure, Carbonsäuren wie Ameisensäure oder Essigsäure, bzw. Sulfonsäuren oder Phsophonsäuren), Basen oder Enzymen, wie beispielsweise in der DE-A 3128478 und der US-A 6,132,558 beschrieben. Bei Verwendung von Säuren als Hydrolysemittel liegen die Vinylamineinheiten der Polymerisate als Ammoniumsalz vor, während bei der Hydrolyse mit Basen die freie Aminogruppen entstehen.In order to prepare polymers containing vinylamine units, preference is given to homopolymers of N-vinylformamide or of copolymers obtained by copolymerizing

• N-vinylformamide with
• Vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, methyl acrylate, ethyl acrylate and / or methyl methacrylate

and subsequent hydrolysis of the homopolymers or the copolymers to form vinylamine units from the copolymerized N-vinylformamide units are obtainable, the degree of hydrolysis usually ≥ 1 and ≤ 100 mol%, preferably ≥ 25 and ≤ 100 mol%, more preferably ≥ 50 and ≤ 100 mol% and particularly preferably ≥ 70 and ≤ 100 mol%, in each case based on the original content of unhydrolysed N-Vinylcarbonsäureamidgruppen. The degree of hydrolysis in the case of the homopolymers corresponds to the content of vinylamine groups in mol%. The hydrolysis of the polymers described above
takes place by known methods by the action of acids (for example, mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, carboxylic acids such as formic acid or acetic acid, or sulfonic acids or Phsophonsäuren), bases or enzymes, such as in the DE-A 3128478 and the US-A 6,132,558 described. When acids are used as hydrolyzing agents, the vinylamine units of the polymers are present as the ammonium salt, while hydrolysis with bases gives rise to the free amino groups.

The degrees of hydrolysis of the homopolymers and copolymers used are preferably mol 85 mol%, advantageously ≥ 95 mol% and particularly preferably 100 mol%. For copolymers, the vinyl esters in copolymerized form, in addition to the hydrolysis of the N-vinyl-formamide units, hydrolysis of the ester groups to form vinyl alcohol units may occur. This is especially the case when carrying out the hydrolysis of the copolymers in the presence of sodium hydroxide solution. Polymerized acrylonitrile is also chemically altered upon hydrolysis. This produces, for example, amide groups or carboxyl groups. The homopolymers and copolymers containing vinylamine units may optionally contain up to 20 mol% of amidine units which are formed, for example, by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with an adjacent amide group, for example of copolymerized N-vinylformamide.

The weight-average molecular weights of the homopolymers or copolymers containing vinylamine units are ≥ 500 and ≦ 10000000 g / mol, preferably ≥ 1000 and ≦ 500000 g / mol and more preferably ≥ 5000 and ≦ 400000 g / mol. These molecular weight ranges correspond in the homopolymers K values in the range of 30 to 250, preferably 60 to 100 (determined according to H. Fikentscher in 5 wt .-% aqueous saline at 25 ° C, a pH of 7 and a polymer concentration of 0.5% by weight).

The homopolymers or copolymers containing vinylamine units can be used both in salt-containing form (corresponding to the hydrolysis mixture obtained) and in salt-free form. Salt-free aqueous solutions of homopolymers or copolymers containing vinylamine units can be prepared, for example, from the salt-containing hydrolysis mixtures described above by means of ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons.

For cost reasons and usually without appreciable losses in the mechanical properties of the moldings, the homopolymers or copolymers containing vinylamine units are frequently in their salt-containing form (ie the homopolymers or copolymers resulting from the hydrolysis of the corresponding N-vinylcarboxamides and not further worked up Mixtures) used.

The polymers containing vinylamine units also include hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, polysaccharides such as starch, oligosaccharides or monosaccharides. The graft polymers are obtainable by free-radically polymerizing, for example, N-vinylformamide in aqueous medium in the presence of at least one of the stated grafting bases together with copolymerizable other monomers and then hydrolyzing the grafted vinylformamide units in a known manner to give vinylamine units.

Typical representatives of the vinylamine homopolymers are known under the trade name Catiofast ^® VFH, Catiofast VSH ^® and Catiofast VMP ^{® ®} or Lupamin 5095, Lupamin 9095 and Lupamin ^{® ®} 1595, BASF SE.

The preparation of the present invention as polyamine A also usable homopolymers or copolymers based on allylamine by free-radical polymerization of allylammonium compounds is for example in the EP-A 95233 disclosed.

With particular advantage, the polyamines A have more than 2 primary amino groups, for example ≥ 3, ≥ 4, ≥ 5, ≥ 6, ≥ 7, ≥ 8, ≥ 9 or even ≥ 10 primary amino groups per mole, in particular ≥ 5 or especially advantageously even ≥ 10 primary amino groups per mole.

Of course, polyamines A also include monosaccharide, oligosaccharide and / or polysaccharide compounds which have ≥ 2 primary amino groups per mole.

According to the invention advantageously polyamines A are used, which at 20 ° C and 1 atm (= 1,013 bar absolute = atmospheric pressure) have a solubility ≥ 5 g, more preferably ≥ 10 g and especially advantageously ≥ 20 g per 100 g of deionized water.

Of course, mixtures of different polyamines A can also be used according to the invention.

Preferred as polyamine A is a vinylamine units homopolymer of a vinylcarboxamide, preferably vinylformamide, having a degree of hydrolysis ≥ 50 mol%, preferably ≥ 85 mol% and particularly preferably 100 mol% and / or a polyethyleneimine having a branched structure.

An essential constituent of the aqueous binder composition according to the invention is, in addition to at least one polyamine A, at least one saccharide compound S.

In the context of this document, a saccharide compound S is understood as meaning monosaccharides, oligosaccharides and / or polysaccharides as well as substitution products and derivatives of the abovementioned compounds.

In this case, the monosaccharides are organic compounds of the general formula C _n H _2n O _n , where n is an integer 5, 6, 7, 8 or 9. These monosaccharides are also referred to as pentoses, hexoses, heptoses, octoses or nonoses, these compounds being subdivided into the corresponding aldoses which contain an aldehyde group or ketoses which have a keto group. Accordingly, the monosaccharides include aldo or ketopentoses, hexoses, heptoses, octoses or nonoses. Preferred monosaccharide compounds according to the invention are the naturally occurring pentoses and hexoses, with glucose, mannose, galactose, fructose, ribose and / or xylose being particularly preferred. Of course, according to the invention, all stereoisomers of all the abovementioned monosaccharides are also included.

It is known that the abovementioned monosaccharides are present in the form of their hemiacetals or ketals, formed from a hydroxy group and the aldehyde or keto group, a five- or six-membered ring being formed as a rule. Now reacts a hydroxy group (from the hemiacetal or Halbketalgruppe or from the carbon skeleton chain) of a Monosaccaridmoleküls with the Halbacetal- or Halbketalgruppe another monosaccharide molecule with dehydration and formation of an acetal or ketal group (such a bond is also called glycosidic compound) thus, disaccharides (having the general empirical formula C _n H _2n-2 O _n-1 ) are obtained. Furthermore, such a disaccharide can react with another monosaccharide with dehydration to a trisaccharide. By further reactions with monosaccharides tetrasaccharides, pentasaccharides, hexasaccharides, heptasaccharides, octasaccharides, nonasaccharides or decasaccharides are obtained. Compounds composed of at least two but not more than ten monosaccharide structural units via glycosidic compounds are referred to as oligosaccharides. Preferred oligosaccharides are the disaccharides, of which the lactose, maltose and / or sucrose are particularly preferred. Of course, according to the invention, all stereoisomers of all the aforementioned oligosaccharides should also be included.

Saccharide compounds which are composed of more than ten monosaccharide structural units are referred to in this document as polysaccharide compounds. The polysaccharide compounds may be composed of the structural elements of a monosaccharide (so-called homoglycans) or the structural elements of two or more different monosaccharides (so-called heteroglycans). Homoglycans are preferably used according to the invention.

Among the homoglycans, the starches composed of α-D-glucose units are particularly preferred. The starches consist of the polysaccharides amylose (D-glucose units which are α-1,4-glycosidically linked together) and amylopectin (D-glucose units which α-1,4- and in addition to about 4% α-1,6 glycosidically linked). Normally, naturally occurring starch contains about 20 to 30% by weight of amylose and about 70 to 80% by weight of amylopectin. By breeding and varying according to plant species, however, the relationship between amylose and amylopectin may be altered. Starches which are suitable are all native starches, such as starches from corn, wheat, oats, barley, rice, millet, potatoes, peas, tapioca or sago. Also of interest are those natural starches which have a high amylopectin content, such as waxy maize starch and waxy potato starch. The amylopectin content of these starches is ≥90% by weight, often ≥95 and ≤100% by weight.

Of course, the term saccharide compound S also includes the substitution products and derivatives of the abovementioned mono-, oligo- and polysaccharide compounds, but excluding those saccharide compounds which have ≥ 2 primary amino groups.

Here, the substitution products of a saccharide compound S are understood as meaning those in which at least one hydroxy group of the saccharide compound S has been functionalized while maintaining the saccharide structure, for example by esterification, etherification, oxidation etc. The esterification is carried out, for example, by reacting the saccharide compound S with inorganic or organic acids , their anhydrides or halides. Of particular interest are phosphated and acetylated saccharide compounds. The etherification is generally carried out by reacting the saccharide compounds with organic halogen compounds, epoxides or sulfates in aqueous alkaline solution. Known ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allyl ethers. The oxidation of at least one hydroxyl group by means of a customary in the organic Kohlenhydatchemie oxidizing agent, such as nitric acid, hydrogen peroxide, ammonium persulfate, peroxyacetic acid, sodium hypochlorite and / or 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), the corresponding keto compound (at Oxidation of a secondary hydroxy group), or carboxyl compound (upon oxidation of a primary hydroxy group).

Derivatives of saccharide compounds S are understood to mean those reaction products of oligosaccharides and polysaccharides which are obtained with cleavage of at least one acetal or ketal group (i.e., at least one glycosidic bond) and therefore degradation of the original saccharide structure. Such degradation reactions are familiar to the person skilled in the art and are carried out in particular by exposing an oligosaccharide or polysaccharide compound to thermal, enzymatic, oxidative and / or hydrolytic conditions.

Starch, cellulose, guar gum, xanthan, alginate, pectin, chitosan, gum arabic, carrageenan, agar and / or gellan as well as substitution products or derivatives thereof are advantageously used as saccharide compound S.

With particular advantage, however, starches and / or starch derivatives or their substitution products are used, with maltodextrin and / or glucose syrup being particularly preferred.

A very common in business practice size to characterize the degree of degradation of starches is the DE value. DE stands for Dextrose Equivalent and denotes the percentage of reducing sugars in the dry matter. The DE value therefore corresponds to the amount of glucose (= dextrose) in grams, which would have the same reducing power per 100 g of dry matter. The DE value is a measure of how far the polymer degradation has taken place. Thus, low DE starches are high in polysaccharides and low in low molecular weight mono- and oligosaccharides, while high DE starches are mainly composed of low molecular weight mono- or disaccharides. The maltodextrins preferred in the context of the present invention have DE values in the range from 3 to 30 and weight-average molecular weights from 15,000 to 30,000 g / mol. A glucose syrup which is likewise preferred in the context of the present invention has DE values of from 20 to 35. Due to the manufacturing process, these products are obtained in the form of aqueous solutions and are therefore usually marketed as such. Suitable solutions of maltodextrins have solids contents of 50 to 70% by weight, and suitable solutions of glucose syrup have solids contents of 70 to 95% by weight. However, maltodextrins are also available in powder form in spray-dried form. Also preferred according to the invention are modified degraded starches which have DE values of from 1 to 3 and weight-average molecular weights of from 100,000 to 1,000,000 g / mol and are usually obtainable as a solid.

The saccharide compound S generally has a molecular weight (mono-, di- or trisaccharides) or weight-average molecular weight (with higher oligo- and polysaccharides) in the range ≥ 150 and ≤ 5000000 g / mol, often in the range ≥ 180 and ≤ 100000 g / mol and often in the range ≥ 180 and ≤ 30000 g / mol.

It is preferred if the saccharide compound S used according to the invention has a solubility of ≥ 10 g, advantageously ≥ 50 g and particularly advantageously ≥ 100 g per liter of deionized water at 20 ° C and atmospheric pressure. According to the invention, however, embodiments are also included, the saccharide compound S having a solubility <10 g per liter of deionized water at 20 ° C and atmospheric pressure. Depending on the amount of these saccharide compounds used, they can then also be present in the form of their aqueous suspension. If according to the invention saccharide compounds S are used in the manner and amount such that they are in aqueous suspension, it is advantageous if the particles of the saccharide compound S suspended in an aqueous medium have an average particle diameter ≦ 5 μm, preferably ≦ 3 μm and particularly preferably ≦ 1 μm exhibit. The average particle diameter is determined as in the case of the aqueous polymer P dispersions by the method of quasi-elastic light scattering (ISO standard 13 321).

Advantageously used according to the invention as at least one saccharide compound is glucose, mannose, galactose, xylose, fructose, ribose, lactose, maltose, sucrose, maltodextrin and / or glucose syrup, but glucose, fructose, maltose, maltodextrin and / or glucose syrup and in particular glucose and / or glucose syrup are particularly preferred.

Of course, mixtures of different saccharide compounds S can also be used according to the invention.

In the aqueous binder according to the invention, the weight ratio of the at least one polyamine A to the at least one saccharide compound S is 1:99 to 80:20, preferably 5:95 to 50:50 and especially preferably 10:90 to 35:65.

The aqueous binder of the invention is prepared by mixing the at least one polyamine A and the at least one saccharide compound S in an aqueous medium at 20 to 25 ° C (room temperature) or at a higher temperature. As a rule, the order of additions is irrelevant.

The resulting aqueous binders generally have a solids content in the range of ≥ 1 to ≦ 70% by weight, based on the sum of the total amounts of polyamine A and saccharide compound S. If the binders according to the invention are used to bind cork particles, their solids content is advantageously ≥ 30 and ≤ 70 wt .-% and particularly advantageously ≥ 50 and ≤ 65 wt .-%. However, if the binders according to the invention are used for bonding glass fibers or glass fiber webs, their solids content is advantageously .gtoreq.5 and .ltoreq.40% by weight and particularly advantageously .gtoreq.10 and .ltoreq.30% by weight, while the binders according to the invention for binding glass or glass fibers Rock wool advantageously have a solids content ≥ 1 and ≤ 15 wt .-% and in particular advantageously ≥ 2 and ≤ 8 wt .-%, wherein the solids content in each case based on the sum of the total amounts of polyamine A and saccharide S.

The aqueous binders according to the invention generally also have a pH in the range ≥ 4 and ≦ 12, advantageously ≥ 5 and ≦ 12 and in particular advantageously ≥ 6 and ≦ 11. The pH is measured at room temperature with a 5 wt .-% (based on the sum of the total amounts of polyamine A and saccharide compound S) aqueous binder with a calibrated pH meter. The adjustment of the pH values is familiar to the person skilled in the art and is carried out by means of inorganic or organic acids and bases, in particular dilute sulfuric acid or aqueous sodium or potassium hydroxide solution.

It is also essential that the aqueous binder according to the invention in addition to the polyamine A and the saccharide compound S as essential components optionally further, familiar to the expert in kind and amount components such as thickeners, pigment dispersers, dispersants, emulsifiers, adhesion promoters, humectants (for example, glycerol) , Buffer substances, neutralizing agents, biocides, defoamers or organic solvents.

However, it is advantageous if the total amount of the organic compounds present in the aqueous binder in addition to the polyamine A and the saccharide compound S is ≦ 30% by weight, preferably ≦ 10% by weight and in particular advantageously ≦ 5% by weight, based in each case on the sum of the total amounts of polyamine A and saccharide compound S, is, but wherein the obtained in the preparation of Vinylamineinheiten homopolymers and copolymers by hydrolysis of the corresponding vinylcarboxylic acid containing end homopolymers and copolymers obtained by-products (direct hydrolysis), such as alkali metal formates or alkali metal acetates the above quantities should not be included.

The aqueous binder according to the invention is advantageously suitable for use as a binder for granular and / or fibrous substrates. Advantageously, therefore, said aqueous binder can be used in the production of shaped articles from granular and / or fibrous substrates.

Granular and / or fibrous substrates are familiar to the person skilled in the art. For example, these are wood chips, wood fibers, cellulose fibers, textile fibers, plastic fibers, mineral fibers such as glass fibers, glass or rock wool, or natural fibers such as jute, flax, hemp or sisal, but also cork particles or sand and other organic or inorganic natural and / or synthetic granular and / or fibrous compounds whose longest extent in the case of granular substrates ≤ 10 mm, preferably ≤ 5 mm and in particular ≤ 2 mm. Of course, the term substrate should also include the fiber webs available from fibers, such as so-called mechanically bonded, for example needled or chemically pre-bonded fiber webs with. The aqueous binder according to the invention is particularly advantageously suitable as a formaldehyde-free binder for the abovementioned mineral fibers, in particular glass fibers, mechanically consolidated or chemically pre-bonded glass fiber webs, as well as for cork particles.

The process for producing a shaped body from a granular and / or fibrous substrate and the abovementioned aqueous binder is advantageously carried out such that the aqueous binder according to the invention is applied to a granular and / or fibrous substrate (impregnation), optionally the treated with the aqueous binder composition ( impregnated) granular and / or fibrous substrate is brought into shape and then the granular and / or fibrous substrate thus obtained a thermal treatment step at a temperature ≤ 110 ° C, preferably ≥ 150 ° C and particularly advantageously ≥ 170 ° C and ≤ 250 ° C, advantageously ≤ 220 ° C, wherein the polyamine A and the saccharide compound S react with each other with dehydration and curing.

It is essential that the essential components of the aqueous binder of the invention, i. the polyamine A and the saccharide compound S, in particular in the form of their aqueous solutions or suspensions, prior to application to the granular and / or fibrous substrate, can be homogeneously mixed. However, it is also possible to mix these two components only immediately before application, for example with a static and / or dynamic mixing device. Of course, it is also possible first to apply an aqueous solution or suspension of the polyamine A and then the aqueous solution or suspension of the saccharide compound S to the granular and / or fibrous substrate, the mixture taking place on the granular and / or fibrous substrate. In an analogous manner, however, it is also possible first to apply the aqueous solution or suspension of the saccharide compound S and then the aqueous solution or suspension of the polyamine A to the granular and / or fibrous substrate. Of course, mixed forms of application of the two essential components should also be included according to the invention.

The impregnation of the granular and / or fibrous substrate is generally carried out in such a way that the aqueous binder agent uniformly on the surface of the fibrous and / or granular substrate is applied. In this case, the amount of aqueous binder is selected so that per 100 g of granular and / or fibrous substrate ≥ 1 and ≤ 100 g, preferably ≥ 2 and ≤ 50 g and particularly preferably ≥ 3 and ≤ 30 g of binder (calculated as the sum of the total amounts of polyamine A and saccharide compound S on a solid basis). The impregnation of the granular and / or fibrous substrate is familiar to the person skilled in the art and takes place, for example, by impregnation or by spraying the granular and / or fibrous substrate with the aqueous binder according to the invention.

After impregnation, the granular and / or fibrous substrate is optionally brought into the desired shape, for example by introduction into a heatable press or mold. Following this, the impregnated granular and / or fibrous substrate in the form of impregnated granules is dried in a manner familiar to the person skilled in the art and cured with dehydration and separation.

Frequently, the drying or curing of the optionally shaped impregnated granular and / or fibrous substrate takes place in two temperature stages, wherein the drying stage at a temperature <100 ° C, preferably ≥ 20 and ≤ 90 ° C and particularly preferably ≥ 40 and ≤ 80 ° C and the curing step at a temperature ≥ 110 ° C, preferably ≥ 150 and ≤ 250 ° C and particularly preferably ≥ 170 and ≤ 220 ° C. After the drying step, the impregnated granular and / or fibrous substrate is still thermoplastic and is still deformable when heated to a temperature ≥ 50 and ≤ 100 ° C. After the curing step with dehydration and separation, the treated granular and / or fibrous substrate usually has a thermosetting behavior.

Of course, it is also possible that the drying step and the curing step of the moldings take place in one step, for example in a molding press.

Mineral fibers, in particular glass fibers or glass fiber fleeces and cork particles, are advantageously used as granular and / or fibrous fibers for the process according to the invention.

The moldings which can be obtained by the process according to the invention have advantageous properties, in particular improved wet tensile strength or improved water resistance. Furthermore, when using the aqueous binder according to the invention for binding glass fibers, glass fiber webs, glass wool or rock wool onto the otherwise customary adhesion promoters, such as silane or siloxane compounds, can be dispensed with, without sacrificing the mechanical properties of the molded articles obtained comes.

Examples I. Preparation of the binder liquors Starting Materials:

Polyamine1 (P1): aqueous solution of polyvinylamine, Mw: 330000 g / mol, degree of hydrolysis 100%, polymer solids content: 9% by weight Polyamine 2 (P2): aqueous solution of polyvinylamine, Mw: 48,000 g / mol, degree of hydrolysis 100%, polymer solids content: 10% by weight Polyamine 3 (P3): aqueous solution of polyvinylamine, Mw: 1200 g / mol, degree of hydrolysis 100%, polymer solids content: 10% by weight Polyamine 4 (P4): Hexamethylenediamine, ≥ 99% by weight, Merck Schuchardt OHG Polyamine 5 (P5): Polyethyleneimine, Mw: 800 g / mol, charge density: 16 meq / g, ≥99 wt% Polyamine 6 (P6): aqueous solution of polyethyleneimine, Mw: 1300 g / mol, charge density: 16 meq / g, polymer solids content: 50 wt% Polyamine 7 (P7): aqueous solution of polyethyleneimine, Mw: 2000 g / mol, charge density: 16 meq / g, polymer solids content: 50 wt% Polyamine 8 (P8): aqueous solution of polyethyleneimine, Mw: 5000 g / mol, charge density: 17 meq / g, polymer solids content: 50 wt% Polyamine 9 (P9): aqueous solution of polyethylenimine, Mw: 750,000 g / mol, charge density: 20 meq / g, polymer solids content: 33% by weight Saccharide Compound 1 (S1): 72% strength by weight aqueous solution of a hydrolytically degraded starch having a DE value of 26 to 32 (C * Sweet 01403 from Cargill GmbH) Saccharide compound 2 (S2): 50% strength by weight aqueous solution of glucose monohydrate (glucose monohydrate from Sigma Aldrich Chemie GmbH) Saccharide compound 3 (S3): Fructose monohydrate ≥99% by weight, Sigma Aldrich Chemie GmbH Saccharide Compound 4 (S4): Maltose monohydrate ≥ 98% by weight, Sigma Aldrich Chemie GmbH Saccharide Compound 5 (S5): 50 wt .-% aqueous solution of a hydrolytically degraded starch having a DE value of 28 (Maltosweet ^® 300, the company Tate and Lyle GmbH) Comparative binder V: Acrodur ^® DS 3530 from BASF SE (50 wt .-% aqueous solution of a mixture consisting of an acrylic acid / maleic acid copolymer and triethanolamine)

Production of the aqueous binder baths

100 g of deionized water and the amounts of the respective polyamines P1 to P9 indicated in Table 1 were initially introduced into a 5 l beaker at 20 to 25 ° C. (room temperature) and then likewise listed in Table 1 with stirring Amounts of the respective saccharide compounds S1 to S5 are added. To these solutions (Momentive Performance Materials Silquest ^® A-1100 silanes of the Fa.) Of 3-aminopropyltriethoxysilane 0.3 g was added and homogeneously mixed by stirring for 10 minutes. Thereafter, the respective solutions were diluted by the addition of deionized water to a polymer solids content of 5 wt .-%. The solutions obtained are referred to as binder liquors A1 to A23. For the binder liquors A11 and A13, a pH of 4 was added by adding 50% strength by weight aqueous sulfuric acid solution and in the case of the binder liquor A12 and A14, a pH of 11 was established by addition of 50% strength by weight aqueous sodium hydroxide solution.

The comparison liquors V1 to V3 were obtained by initially charging 180.0 g of the comparative binder V in a 5 l beaker and then adding 0.3 g of 3-aminopropyltriethoxysilane and homogeneously mixing by stirring for 10 minutes. Thereafter, the respective solutions were diluted by the addition of deionized water to a polymer solids content of 5 wt .-%. In the comparison liquor V2, a pH of 4 was added by addition of 50% strength by weight aqueous sulfuric acid solution and in the case of the binder liquor V3, a pH of 11 was established by addition of 50% strength by weight aqueous sodium hydroxide solution. Table 1: Composition of the binder baths binder liquor polyamine saccharide A1 100.0 g P1 112.5 g S1 A2 200.0 g P1 100.0 g S1 A3 400.0 g P1 50.0 g S1 A4 200.0 g P1 144.0 g S2 A5 200.0 g P1 73.0 g S3 A6 200.0 g P1 73.0 g S4 A7 200.0 g P1 144.0 g S5 A8 200.0 g P2 111.1 g of S1 A9 200.0 g P3 111.1 g of S1 A10 40.0 g P4 88.9 g S1 A11 100.0 g P1 112.5 g of S1 (pH 4) A12 100.0 g P1 112.5 g of S1 (pH 11) A13 200.0 g P1 100.0 g of S1 (pH 4) A14 200.0 g P1 100.0 g S1 (pH 11) A15 18.2 g P5 100.0 g S1 A16 36.0 g P6 100.0 g S1 A17 36.0 g P7 100.0 g S1 A18 36.0 g P8 100.0 g S1 A19 54.5 g P9 100.0 g S1 A20 63.0 g P8 81.3 g S1 A21 18.0 g P8 162.0 g S2 A22 36.0 g P8 144.0 g S2 A23 63.0 g P8 117.0 g S2

II. Application studies

To produce the moldings, microfiber nonwoven fabrics (27 cm x 28.5 cm) from Whatman, type GF / A no. 1820-915 used with a basis weight of 54 g / m ² .

Production of the test strips

To apply the binder baths (impregnation), the glass fiber webs were passed in the longitudinal direction over an endless PES wire belt at a belt speed of 60 cm per minute through the aforementioned 5 wt .-% aqueous binder liquors A1 to A23 and V1 to V3. By subsequent suction of the aqueous binder liquors, the wet application to 216 g / m ² (corresponding to 10.8 g / m ² binder calculated as a solid) was set. The impregnated glass fiber webs thus obtained were dried in a Mathis oven on a plastic mesh carrier for 3 minutes at 180 ° C and at 200 ° C at maximum hot air flow and cured. After cooling to room temperature test strips were sized with a size of 240 mm x 50 mm in the fiber longitudinal direction. The test strips obtained were then stored for 24 hours at 23 ° C and 50% relative humidity in a climate chamber. The glass fiber nonwoven test strips obtained as a function of the binder liquors A1 to A23 and V1 to V3 used are referred to below as test strips A1 to A23 and also to V1 to V3.

Determination of the tensile strength "dry" at room temperature (= dry tensile strength, TRK)

The tensile strength at room temperature was determined on a tensile testing machine from Zwick-Roell, type Z005. The test strips A1 to A23 and V1 to V3 were introduced vertically so a jig that the free clamping length was 200 mm. Subsequently, the clamped test strips were pulled apart at a rate of 25 mm per minute in the opposite direction to the crack of the test strips. The higher the force required to tear the test strips, the better the corresponding tear strength is to be evaluated. There were 5 separate measurements each. The TRK values given in Table 2 each represent the average of these measurements.

Determination of the tensile strength "wet" at 80 ° C (= wet tensile strength, NRK)

To determine the wet tensile strength, the test strips A1 to A23 and V1 to V3 were stored for 15 minutes at 80 ° C in deionized water and then dabbed off excess water with a cotton fabric. The wet tensile strength was determined on a tensile testing machine from Zwick-Roell, type Z005. The test strips A1 to A23 and V1 to V3 were introduced vertically so a jig that the free clamping length was 160 mm. Subsequently, the clamped test strips were pulled apart at a rate of 25 mm per minute in the opposite direction to the crack of the test strips. The higher the force required to crack the test strip, the better the corresponding wet tensile strength is to be evaluated. There were 5 separate measurements each. The NRK values given in Table 2 each represent the average of these measurements.

Determination of tensile strength at 180 ° C (= hot tensile strength, HRK)

The tensile strength at 180 ° C was determined in the tensile testing machine Zwick-Roell, type Z 010 TH2 A. The test strips A1 to A23 and V1-V3 were introduced vertically into a clamping device so that the free clamping length was 240 mm. The determination of the tensile strength was carried out such that the test strips A1 to A23 and V1 to V 3 first tempered for 60 seconds at 180 ° C and then at this temperature at a rate of 25 mm per minute in the opposite direction to the crack of the test strip were pulled apart. There were 5 measurements each. The HRK values also given in Table 2 each represent the average of these measurements. Table 2: Summary of Tearing Results [Figures in N / 50mm] TRK NRK HRK Test strips 180 ° C 200 ° C 180 ° C 200 ° C 180 ° C 200 ° C V1 109 99 60 90 104 104 V2 103 97 32 54 101 103 V3 40 31 3 4 71 75 A1 100 103 37 40 97 109 A2 108 98 57 60 103 99 A3 106 112 62 - 111 100 A4 98 90 70 - 101 92 A5 90 91 64 - 97 93 A6 92 91 70 - 103 102 A7 91 97 53 - 100 102 A8 98 101 64 73 104 112 A9 86 93 46 56 94 101 A10 92 - 31 - 80 - A11 - - 37 41 - - A12 - - 45 47 - - A13 - - 56 61 - - A14 - - 62 68 - - A15 - 108 - - - 106 A16 - 104 - - - 106 A17 - 107 62 - - 98 A18 98 99 47 54 95 98 A19 - 97 - 93 A20 101 104 57 59 97 93 A21 - 112 - 71 - 102 A22 115 112 73 79 106 105 A23 119 110 74 78 101 107

It can be clearly seen from the results that the aqueous binders according to the invention have similar or better tear strength results than the binder systems of the prior art.

Claims (15)

Aqueous binder for granular and / or fibrous substrates containing as active ingredients a) at least one organic compound which has at least two primary amino groups [polyamine A], and b) at least one saccharide compound S, wherein c) the weight ratio of the at least one polyamine A to at least one saccharide compound S is 1:99 to 80:20. An aqueous binder according to claim 1, wherein monosaccharides, oligosaccharides and / or polysaccharides and their substitution products or derivatives are used as saccharide compounds. An aqueous binder according to claim 1 or 2, wherein at least one saccharide compound S is glucose, mannose, galactose, xylose, fructose, ribose, lactose, maltose, sucrose, maltodextrin and / or glucose syrup. An aqueous binder according to any one of claims 1 to 3, wherein the at least one polyamine A has a molecular weight ≥ 60 and ≤ 10000000 g / mol. An aqueous binder according to any one of claims 1 to 4, wherein the at least one polyamine A has ≥ 5 primary amino groups per mole. The aqueous binder according to claim 5, wherein the polyamine A is a vinylamine units homopolymer of a vinylcarboxamide having a degree of hydrolysis ≥ 50 mol% and / or a polyethylenimine having a branched structure. An aqueous binder according to any one of claims 1 to 6, wherein the weight ratio of the at least one polyamine A to the at least one saccharide compound S is 5:95 to 50:50. An aqueous binder according to any one of claims 1 to 7, wherein the total amount of the present in addition to the polyamine A and the saccharide compound S in the aqueous binder organic compounds ≤ 30 wt .-%, based on the sum of the total amounts of polyamine A and saccharide compound S. An aqueous binder according to any one of claims 1 to 8, wherein the pH is in the range ≥ 6 and ≤ 11. An aqueous binder according to any one of claims 1 to 9, wherein the solids content is ≥ 1 and ≤ 70 wt .-%, based on the sum of the total amounts of polyamine A and saccharide compound S. Use of an aqueous binder according to any one of claims 1 to 10 for the production of moldings from granular and / or fibrous substrates. Process for the production of a shaped body from granular and / or fibrous substrates, characterized in that an aqueous binder according to one of Claims 1 to 10 is applied to the granular and / or fibrous substrate, optionally the granular and / or fibrous substrate treated with the aqueous binder Substrate is brought into shape and then the thus treated granular and / or fibrous substrate is subjected to a thermal treatment step at a temperature ≥ 110 ° C. A method according to claim 12, characterized in that per 100 g of granular and / or fibrous substrate ≥ 1 and ≤ 100 g of binder (calculated as the sum of the total amounts of polyamine A and saccharide compound S on a solids basis) are used. A method according to claim 12 or 13, characterized in that are used as granular and / or fibrous substrates mineral fibers or cork particles. Shaped body obtainable by a process according to one of claims 12 to 14.